This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (
Although the field of passive sampling to measure freely dissolved concentrations in sediment porewater has been sufficiently advanced for organic compounds in the low- to midrange of hydrophobicity, in situ passive sampling of strongly hydrophobic polychlorinated biphenyls (PCBs) is still challenged by slow approach to equilibrium. Periodic vibration of polyethylene (PE) passive samplers during exposure has been previously shown to enhance the mass transfer of polycyclic aromatic hydrocarbons (PAHs) from sediment into PE. Herein, we used a new vibrating platform, developed based on our earlier platform design, to demonstrate the effectiveness of periodic vibration for strongly hydrophobic compounds such as hexa-, hepta-, and octachloro-PCBs. Uptake of PCBs in PE after 7, 14, 28, and 56 days under different vibration modes was compared to that under static and mixed laboratory deployments. All PCBs reached within 95-100% of equilibrium after 56 days of deployment in the system vibrated briefly every 2 min, while none of the congeners achieved more than 50% of equilibrium in static deployment for the same period. Periodic vibration also increased the dissipation rate of four performance reference compounds (PRCs) from passive samplers. Higher fractional loss of PRCs and closer approach to equilibrium in the vibrated deployment resulted in estimation of corrected porewater concentrations that were statistically indistinguishable from the true equilibrium values even after a short 7-day deployment. Porewater concentrations of the strongly hydrophobic PCB congeners were overestimated by up to an order of magnitude in the static passive sampler after the same deployment time.
Passive sampling for the measurement of freely dissolved concentrations of organic pollutants in sediment porewater has emerged as a promising approach, but in situ measurements are complicated by slow mass transfer of strongly hydrophobic compounds. The primary resistance to mass transfer arises in the sediment side where a concentration depletion layer develops in the vicinity of the polymeric passive sampling material. The slow mass transfer results in underequilibrated passive sampler measurements that need to be corrected for equilibrium, typically by extrapolation of the loss kinetics of performance reference compounds. Such corrections are prone to large errors, especially when deviation from equilibrium is large. In this research we address the challenge of slow mass transfer by disrupting the external depletion layer around an in situ passive sampler. We report an engineering innovation of adapting low-cost vibration motors for periodically disrupting the depletion layer in a passive sampler deployed in sediments. The uptake of 16 polycyclic aromatic hydrocarbons into polyethylene passive samplers was measured after 7, 14, 28, and 56 days of exposure to sediment under static, vibrating, and fully mixed modes. We demonstrate through laboratory experiments and numerical mass transfer modeling that short periodic shaking of a passive sampler deployed in static sediment enhances the rate of mass transfer and reduces the difference in the extent of equilibrium achieved compared to a well-mixed laboratory equilibrium. The improvement over static sediment deployment is especially evident for the high molecular weight compounds such as benzo(a)pyrene.
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